S,s-dialkyl-n-substituted phosphoroamidodithionites

ABSTRACT

WHEREIN R1 and R2 are independently alkyl of one to eight carbon atoms, or alkenyl of two to eight carbon atoms, R3 is hydrogen or alkyl of one to four carbon atoms, and R4 is hydrogen, alkyl of one to four carbon atoms, alkenyl of two to four carbon atoms, aryl of six to 15 carbon atoms optionally substituted with halogen atoms or alkyl groups of one to four carbon atoms or an acyl group of two to four carbon atoms, with the proviso that R3 and R4 may be joined to form an alkylene radical of two to five carbon atoms. The compounds possess insecticidal and herbicidal activity.   Compounds of the formula

Uited States Patent [191 Freenor, H11

[451 Aug. 27, 1974 S,S-DIALKYL-N-SUBSTITUTED PHOSPHOROAMIDODITHIONITES [75] Inventor: Francis J. Freenor, 111, Richmond,

[21] Appl. No.: 219,559

Primary Examiner-Anton H. Sutto Attorney, Agent, or Firm-G. F. Magdeburger; John Stoner, J r.; Raymond Owyang [57] ABSTRACT Compounds of the formula m s R4 wherein R and R are independently alkyl of one to eight carbon atoms, or alkenyl of two to eight carbon atoms, R is hydrogen or alkyl of one to four carbon atoms, and R is hydrogen, alkyl of one to four carbon atoms, alkenyl of two to four carbon atoms, aryl of six to 15 carbon atoms optionally substituted with halogen atoms or alkyl groups of one to four carbon atoms or an acyl group of two to four carbon atoms, with the proviso that R and R may be joined to form an alkylene radical of two to five carbon atoms. The compounds possess insecticidal and herbicidal activity.

8 Claims, N6 Drawings S,S-DIALKYL-N-SUBSTITUTED PHOSPHOROAMIDODITHIONITEQ BACKGROUND OF THE INVENTION 1. Field The present invention is directed to phosphoroamidodithionites, more particularly S,S-dialkyl- N-monoand di-substituted phosphoroamidodithionites and their use as insecticides and/or herbicides.

DESCRIPTION OF THE INVENTION Compounds of the present invention may be represented by the formula RrS R3 preferably alkenyl of two to four carbon atoms, R ishydrogen or alkyl of one to four carbon atoms, R; is hydrogen, alkyl of one to four carbon atoms, alkenyl of two to four carbon atoms, aryl of six to 15 carbon atoms substituted with zero to five halogen atoms of atomic number 9 to 35 or alkyl groups of one to four carbon atoms, or an acyl group of two to four carbon atoms, with the proviso that R and R may be joined to form an alkylene radical of two to five carbon atoms, preferably four to five carbon atoms.

The aryl groups which R, may represent are preferably benzyl or phenyl, either being substituted with zero to five halogen atoms of atomic number 9 to 35 or alkyl groups of one to four carbon atoms. More preferably, R is phenyl substituted with zero to two halogen atoms of atomic number 9 to 17 or alkyl of one to two carbon atoms, and still more preferably, phenyl substituted with zero to one chlorine or fluorine atom.

Representative alkyl groups which R,, R R and R may represent include methyl, ethyl, n-propyl, isopropyl, butyl, t-butyl, etc. Representative alkenyl groups which R R and R may represent include vinyl, allyl, crotyl, etc. R and R may also be pentyl, hexyl, octyl, etc. Preferably R and R will be the same, or will be alkyl. R is preferably alkyl or aryl optionally substituted as the case may be.

Representative aryl groups which R, may represent include phenyl, naphthyl, benzyl, o-chlorophenyl, fluorophenyl, o-bromophenyl, p-fluorophenyl, mchlorophenyl, o-methylphenyl, p-butylphenyl, obutylphenyl, o,pdichlorophenyl, pentachlorophenyl, o-chloro-p-methylphenyl, o-fluoro-m-chlorophenyl, 2-chloronaphthyl, etc.

Representative radicals which R and R joined together with nitrogen may represent include piperidyl, pyrrolidyl and morpholine.

Representative acyl groups which R, may represent include acetyl, propionyl and butyryl.

Representative compounds of the present invention include S,S-dimethyl-N-butyl phosphoroamidodithionite, S,S-dimethyl-N-phenyl phosphoroamidodithionite, S,S-diethyl-N,N-dimethyl phosphoroamidodithionite, S,S-dimethyl-N-acetyl phosphoroamidodithionite,

2 S-methyl-Sethyl-N-isopropyl phosphoroamidodithionite, S-methyl-S-ethyl-N-vinyl phosphoroamidodithionite, S,S-diethyl-N,N-diethyl phosphoroamidodithionite, S,S-diisopropyl-N-methyl phosphoroamidodithionite, S,S-n-butyl phosphoroamidodithionite, S-methyl- S-hexylN-ethyl-N-propionyl phosphoroamidodithionite, S-propyl-S-allylN-methyl-N-phenyl phosphoroamidodithionite, S-methyl-S-vinyl N-methyl phosphoroamidodithionite, S,S-dipropyl- N-2-chlorophenyl phosphoroamidodithionitc, S,S-dibutyl-N-2,4-di-chlorophenyl phosphoroamidodithionite, S,S-dibutyl-N-2-ethylphenyl phosphoroamidodithionite, S,S-diethyl-N-ethyl-N-2- naphthyl. phosphoroamidodithionite, S,S-dibutyl-N- pentachlorophenylphosphoroamidodithionite, S,S- dibutyl-N-2,4-dichloro-3,S-dimethylphenyl phosphoroamidodithionite, S,S-dibutyl-N-piperidyl phosphoroamidodithionite, S,S-dibutyl-N-pyrrolidyl phosphoroamidodithionite, etc.

The compounds of the present invention are prepared by the reaction of an appropriate S,S-diuliphutic hydrocarbyl phosphorus halide with ammonia with a suitable amine or with an appropriate amide according to the following reaction:

RiS Rs /PX HN wherein R R R and R are as indicated above and X is a halogen, preferably chlorine.

Generally, the reaction is accomplished by adding the ammonia or amine slowly to the phosphorus chloride. Preferably an excess, e.g., up to twice the molar amount of ammonia, amide or the amine can be used. The excess reactant acts as a base acceptor to react with the evolved l-IX and thereby neutralize it. The reaction is preferably carried out in the presence of an inert solvent, such as methylene chloride ether, benzene, hexane, etc. Also a molecular seive is preferably present which serves as a drying agent for the solvent amine. The amount of molecular seive should be enough to assure substantially complete removal of any H O.

When ammonia is reacted with the phosphorus chloride it is generally preferable to dissolve the ammonia in the solvent and then add the phosphorus chloride to the ammonia-solvent mixture. When an amine is used, the solvent is preferably added to the phosphorus chloride and the amine added slowly to the phosphorus chloride-solvent mixture.

The above reaction is preferably carried out at a temperature from 78 to 30C. Following the reaction, the product can be recovered by conventional means. Thus the reaction mixture may be stripped of solvent, the product washed with water and dried over magnesium sulfate.

The phosphorus chloride is known in the art and can be prepared as for example by the procedure in U.S. Pat. No. 3,210,244. Thus a suitable mercaptan may be reacted with phosphorus trichloride to give the S,S- dialiphatic hydrocarbyl phosphorus chloride. If different alkyl or alkenyl groups are desired, two different mercaptans can be reacted with the phosphorus trichloride.

The present invention can be more fully understood by reference to the following examples.

Example 1 chloride was dissolved in approximately 150 ml. of methylene dichloride. A small number of molecular sieves were added. Piperidine, 4.06 g. (0.05 mole) was added slowly. The reaction mixture was cooled in an Preparation of S,S-di-n-butyl phosphoroamidodithio- 5 ice bath during the reaction. The reaction mixture was nite permitted to stand overnight after which it was filtered Ammonia (large excess based on the amount f S,S- and evaporated down to obtain a yellow oil which was dibutyl phosphorus chloride) was di lv d i th then dissolved in methylene dichloride, washed twice lene dichloride, cooled to dry ice t t A ll with water and dried over magnesium sulfate. After 150- number of molecular sieves were added. S,S-dibutyl l 131101111116 Chemical analysls Showed: phosphorus chloride, 6.5 g. (0.03 mole), was then added slowly. A solid white precipitate resulted. The

Calculated Found react1on mixture was slowly warmed up to room temperature and left standing approximately 48 hours. The 21- white solid was removed and the remaining solution P stripped to obtain an oil having the following analysis:

Example 4 Preparation of S,S-di-n-butyl-N-acetyl phoshoroamidodithionite c 1 1 d F d p a cu aw Under a nitrogen atmosphere, 50 ml. of diethyl ether N was dried over several molecular sieves. Then, 9.15 g. (0.0373 mole) of S,S-di-n-butyl phosphorus chloride was added to the dry ether. Next, 2.21 g. (0.0373 mole) Example 2 of acetamide was added and the reaction mixture turned cloudy. Triethylamine, 3.78 g. (0.0373 mole) preparatlon phos' was added dropwise. A white precipitate formed, and phoroamdodlthlomte the reaction mixture was stirred for 1 hour at ambient 100 of methylene m plus a Small temperature. After warming, the reaction mixture was of molecular sieves were mixed with l3.05 g. of S,S-di- 3O Stirred for 24 y Phosphorus Chlonde: Dlethyl amme The white precipitate was removed by filtration. The was added X' The resultmg Slurry was resulting solution slowly formed two layers. After stand for approxlmately. 24 hoursh resumng days the layers were separated. The upper layer ture was filtered and strlpped to obtam a colorless 011 weighed 530 grams Analysis; which on chemical analysis showed:

Calculated Found Calculated Found 5 24.0 26.3 57 21 3L7 P% 11.6 13.8 P '7. 1 1.01 11.8 40

The NMR spectra was consistent with the assigned E 1 3 structure. The infrared spectra had adsorption peaks at e 5.85, 6.85, 7.25, 7.85, 8.1, 8.3 and 13.4 microns. Pr p r i n of -bUIyl-N-pyrrolidyl phos- Other compounds of the present invention were prephoroamidodithionite pared substantially as described above and are reported 5.84 g. (0.024 mole) of S,S-di-n-butyl phosphorus in Table 1. All of the compounds are oils.

TABLE 1 Elemental Analysis "/r Ex. 5 P Halogen No. Compound Calculated Found Calculated Found Calculated Found 5 S,S-n-hutyl-N.N-di-n-propyl 20.7 20.7 10.0 10.0

phosphoroamidodithionite 6 S,S di-n-hutyl-N,N-dimcthyl 25.3 25.1 12.2 1 1.8

phosphoroamidodithionitc 7 S,S-di-n-butyl-N-methyl 5.8 53* phosphoroamidodithionitc 8 S,S-di-n-butyl-N,N-di-n-buty1 19.0 19.0 9.2 8.8

phosphoroamidodithionitc 9 S.S-diisopropyl-N,N-diethyl 12.2 1 1.8

phosphoroumidodithionite l0 S,S-diisopropyl-N.N di-N-propyl 22.8 22.3 1 1.0 10.6

phosphoroamidodithionitc 1 l S,S-di-n-butyl-NM-chlorophenyl 10.6 10.5"

phosphoroamidodithionitc 12 S,S-di-n-buty1-N-2fluoropheny1 6.0* 6.2

phosphoroamidodithionite 13 S,S-diisopropyl-N-4-chlorophenyl 1 1.5" 9.8 10.1 9.2

phosphoroamidodithionitc l4 S,S-diisopropyl-NQ-fluorophenyl 22.0 21.8 1 1.6 1 1.0

phosphoroamidodithionite TABLE I- Continued Elemental Analysis "/1 Ex. S P Halogen No. Compound Calculated Found Calculated Found Calculated Found S,S-diisopropyl-N,N-di-n-butyl 20.7 18.6 10.0 9.2

phosphoroamidodithionite 16 S,S-diisopropyl phosphoroamido- 7.1* 6.6*

dithionite 17 S,S-diisopropyl-N-methyl 6.6* 6.1

phosphoroamidodithionite l8 S,S-diisopropyl-N-ethyl 28.5 27.0 13.7 12.8

phosphoroamidodithionite 1) S,S diihnpmpyl-N-n-buly1 25.3 23.8 12.2 11.6

plans honmmidodithionite 20 5,3 l icthyl N,N4licthyl 28.5 25.6 13.8 13.0

plumph:mnnnirlmlithionllc '21 5,5 dictliyl N,N'di'n'lmlyl 211.5 25.4 13.11 12.1

pliosplmrmnnitlndilliimiilc 22 3.5 tliclhyl-N.N-tlirnc1hyl 32.5 30.0 15.7 14.)

phosphormimiduditliionitc Z3 S,S-dicthyI-N-cthyl 32.5 29.6 15.7 14.6

phosphoronmidodithionitc 24 S.S-di-n-huty1-N-henly1 20.4 18.4 9.8 9.1

phosphoroamidodithionile 25 S.S-di-n-butyl-N-ally1 24.2 21.9 1 1.7 10.6

phosphoroamidodithionite 26 S.S-dim-propyl-N.N-dicthyl 25.3 23.6 12.2 1 1.3

phosphoroamidodithionite 27 S.S-di-n-propyl-N-n-butyl 5.3 25.1 12.2 1 1.3

phosphoroumidodithionite 28 S.S-di-n-propyl-N.N-dimethyl 28.5 27.5 13.8 12.5

phosphoroamidodithionite 29 S,S-di-n-propylN-methyl 30.4 30.3 14.6 14.8

phosphoroamidodithionite 30 S.S-di-n-propyl-N-piperidyl 24.2 21.9 1 1.7 10.6

phosphoroamidodithionite 31 S,S-di-n-propyl-N,N-di-n-propyl 22.8 21.1 1 1.0 10.4

phosphoroamidodithionite 32 S.S-di-n-propyl-N-benzyl 22.3 22.5 10.8 10.4

phosphoroamidodithionite 33 S.S-di-n-propyl-N-allyl 27.1 23.9 13.1 13.0

phosphoroamidodithionitc 34 S.S'di-n-propyLN-2-fluorophenyl 22.0 20.0 10.6 10.5

phosphoroamidodithionite 35 S,S-din-propyl-N-ethy1 28.5 29.0 13.8 13.6

phosphoroamidodithionite 36 S,S-di-n-propy1-Nnbutyl 20.7 20.5 10.0 10.0

phosphoroamidodithionite 37 S.S-di-n-octylN-methy1 18.2 17.6 8.8 8.2

phosphoroamidodithionite 38 S.S-di n-octyl-N piperidyl 15.8 14.8 7.6 7.2

phosphoroumidodithionitc 39 S.S-di-n-octyl'N-butyl 16.3 1 5.0 7.9 7.7

phosphoroamidodithionite 40 S.S-di-npropyl-Nmcetyl-N- 20.3 21.3 9.9 10.4

phenyl phosphoroamidodithionitc 41 S,S-di-mpropyl-N-acetyl 26.8 26.3 13.0 12.1

phosphoroamidodithionite 42 S.S-diipropyl-N-butyryl 24.0 23.6 1 1.6 1 1.

phosphoroamidodithionitc 43 S,S-di-i-propy1-N-acetyl 12.9 1 1.8 0.0** 0.19

phosphoroamidodithionite 44 S.S-di-nhutylN-propionyl 10.5 10.9 4.7" 3.2*

phosphoroumidodithionitc nitrogen halogen The compounds of the present invention are, in general, herbicidal in both preand post-emergence applications. For preemergence control of undesirable vegetation these compounds will be applied in herbicidal quantities to the environment, e.g., soil infested with seeds and/or seedlings of such vegetation. Such application will inhibit the growth of or kill the seeds, germinating seeds and seedlings. For post-emergence applications the compounds of the present invention will be applied directly to the foliage and other plant parts. Generally they are effective against weed grasses as well as broadleaved weeds. Some may be selective with respect to type of application and/or type of weed.

Preand post-emergence herbicidal tests on representative compounds of this invention were made using the following methods:

Pre-Emergence Test An acetone solution of the test compound was prepared by mixing 750 mg. compound, 220 mg. of a nonionic surfactant and 25 ml. of acetone. This solution was added to approximately 125 m1. of water containing 156 mg. of surfactant.

Seeds of the test vegetation were planted in a pot of soil and the compound solution was sprayed uniformly onto the soil surface at a dose of micrograms per cm The pot was watered and placed in a greenhouse. The pot was watered intermittently and was observed for seedling emergence, health of emerging seedlings, etc. for a 3-week period. At the end of this period the herbicidal effectiveness of the compound was rated based on the physiological observations. A 0 to 100 scale was used; 0 representing no phytotoxicity, 100 representing complete kill.

Post-lmergence Test The test compound was formulated in the same manner as described above for the pre-emergence test. The concentration of the compound in this formulation was 5000 ppm. This formulation was uniformly sprayed on The amount of compound administered will vary with the particular plant part or plant growth medium which is to be contacted, the general location of application, i.e., sheltered areas such greenhouses as compared to exposed areas such as fields, as well as the desired type of control. For pre-emergent control of most plants dosages in the range of about 0.5 to lbs. per acre will be used. Such administration will give a concentration of about 2 to 80 ppm. compound distributed throughout 0.l acre-foot. For post-emergence application, such as foliar spray application, compositions containing about 0.5 to 8 lbs. compound per 100 gal. spray will be used. Such application is equivalent to about 0.5 to 20 lbs. compound per acre.

The herbicidal compositions of this invention comprise a herbicidal amount of one or more of the above described compounds intimately admixed with a biologically inert carrier. The carrier may be a liquid diluent such as water or acetone or a solid. The solid may be in the form of dust powder or granules. These compositions will also usually contain adjuvants such as a wetting or dispersing agent to facilitate their penetration into the plant growth media or plant tissue and generally enhance their effectiveness. These compositions may also contain other pesticides, stabilizers, conditioners. fillers and the like.

The compounds of the present invention also possess insecticidal activity. Representative compounds were tested as follows to illustrate the insecticidal properties. The test results are reported in Table III. Test Procedures Two-spotted Mites (Tetranyclius urticae): An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to 100 ppm. Pinto bean leaves which were infested with mites were dipped in the toxicant solution. Mortality readings were taken after 24 hours.

Two-spotted Mite Eggs (Tetranychus urticae): An Acetone solution of the candidate toxicant was prepared containing a small amount of nonionic surfactant. The acetone soluton was diluted with water to give a 100 ppm solution. A primary leaf from Pinto beans which had been infested with mites 48 hours before and consequently contained mite eggs was immersed in the toxicant solution and then allowed to dry at room temperature for 7 days at 85F. On the eighth day the egg mortality was rated on a scale of 0 to 11; 0 representing no kill, ll representing 100% kill.

Aphids (Aphis gossypii Glover): An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to ppm. Cucumber leaves infested with the cotton aphids were dipped in the toxicant solution. Mortality readings were then taken after 24 hours.

TABLE III "/1 Control Two-spotted Two-spotted Mites Compound Mites Eggs Aphids S.S-di nbutyl-N.N-dimethyl 96 phosphoroamidodithionite S.S-n-butyl-N.N-di-n-propyl l00 phosphoroamidodithionite S.S-di-n-butyl 98 phosphoroamidodithionite S.S-di-n-butylNmethyl 99 99 phosphoroamidodithionite S.S-di-n butyI-N-2-fluorophenyl 96 phosphoroamidodithionite S.S-diisopropylN-methyl 98 phosphoroamidodithionite S.S-diisopropyl-N-ethyl 100 96 phosphoroamidodithionite S.S-diethyl-N-ethyl phosphoroamidodithionite S.S di-n-propyl N.N-diethyl 97* 100 phosphoroarnidodithionite S.S-di-n'propyl-N.N-dimethyl I00 100 phosphoroamidodithionite S.Sdi-n-propy|-N-methyl I00 I00 phosphoroamidodithionite S.S-di-n-propyl-N-piperidyl 96 phosphoroamidodithionite S.S-di-n-propyl'N.N-di-n-propyl 99 99 phosphoroamidodithionite ss-di n-propyl-N-benzyl I00 99 phosphoroamidodithionite S.S-di-n-propylN-allyl 99 phosphoroamidodithionite S.S-di-n-propyl-N-2-fluorophenyl 70 I00 phosphoroamidodithionite S.S-di-n-propyl-N-ethyl [00 9O 94 phosphoroamidodithionite S.S-din-butyl-N-acetyl 96 96 94 phosphoroamidodithionite S S-di-nbutyl-N-propi0nyl 98 phosphoroamidodithionite S.S-di-n-pr0pyl-N-acetyl I00 100 I00 phosphoroamidodithionite S.S-di-n-propyl-N-acetyl-N-phenyl 100 96 phosphoroamidodithionite In general, the preferred compounds for use as insecticides are those wherein R, and R are individually propyl or butyl, R is hydrogen, methyl. ethyl or propyl and R is hydrogen, methyl, ethyl, propyl or fluorophenyl; or benzyl or allyl when R, and R are propyl.

In addition to the specific formulations and application techniques described above, one or more of the compound derivatives of the invention may be applied in other liquid or solid formulations to the insects, their environment, or hosts susceptible to insect attack. For example, they may be sprayed or otherwise applied directly to plants or soil so as to effect control of insects coming into contact therewith.

Formulations of the compounds of this invention will comprise a toxic amount of one or more carbamate derivatives and a biologically inert carrier. Usually they will also contain a wetting agent. Solid carriers such as clay, talc, sawdust and the like may be used in such formulations. Liquid diluents which may be used with these compounds include water and aromatic solvents. In addition these formulations may contain other compatible pesticides. plant growth regulators, fillers, stabilizers, attractants and the like.

The concentration of the active ingredients to be used with inert carriers, either solid or liquid carriers, will be dependent upon many factors, such as the particular carbamate compound which is used, the carrier in or upon which it is incorporated, the method and conditions of application, the insect species to be controlled, etc., the proper consideration of these factors being within the skill of these versed in the art. In genera], the toxic ingredients of this invention will be effective in concentrations from about 0.000] percent by weight to as high as 90 percent by weight or higher. Economically, of course, it is desirable to use lower concentrations of this active ingredient. Thus, it is usually desirable to use less than 20 percent by weight of the active ingredient in a particular composition.

The terms insecticide and insect as used herein refer to their broad and commonly understood usage rather than to those creatures which in the strict biological sense are classified as insects. Thus, the term insect" is used not only to include small invertebrate animals belonging to the class lnsecta but also to other related classes of arthropods whose members are segmented invertebrates having more or fewer than six legs, such as spiders, mites, ticks, centipedes, worms and the like.

Some of the compounds of the present invention are also useful in the control of nematodes and algae, for example Euglena.

As will be evident to those skilled in the art, various modifications on this invention can be made or followed, in the light of the foregoing disclosure and discussion, without departing from the spirit or scope of the disclosure or from the scope of the following claims.

I claim:

1. Compound of the formula wherein R and R are independently alkyl of one to eight carbon atoms, R;, is hydrogen or alkyl of one to four carbon atoms and R, is hydrogen or alkyl of one to four carbon atoms.

2. Compound of claim 1 wherein R and R are independently alkyl of one to four carbon atoms.

3. Compound of claim 1 wherein R and R are independently alkyl of three to four carbon atoms.

4. Compound of claim 1 wherein R and R are the same and are alkyl of one to four carbon atoms.

5. Compound of claim 1 wherein R and R are the same and are alkyl of one to four carbon atoms, R, is hydrogen and R, is alkyl of one to four carbon atoms.

6. S,S-di-n-butylphosphoroamidodithionite, according to claim 1.

7. S,S-di-n-butyl-l\l-methylphosphoroamidodithionite, according to claim 6.

8. S.S-di-n-propyl-N-methylphosphoroamidodithionite, according to claim 6. 

2. Compound of claim 1 wherein R1 and R2 are independently alkyl of one to four carbon atoms.
 3. Compound of claim 1 wherein R1 and R2 are independently alkyl of three to four carbon atoms.
 4. Compound of claim 1 wherein R1 and R2 are the same and are alkyl of one to four carbon atoms.
 5. Compound of claim 1 wherein R1 and R2 are the same and are alkyl of one to four carbon atoms, R3 is hydrogen and R4 is alkyl of one to four carbon atoms.
 6. S,S-di-n-butylphosphoroamidodithionite, according to claim
 1. 7. S,S-di-n-butyl-N-methylphosphoroamidodithionite, according to claim
 6. 8. S,S-di-n-propyl-N-methylphosphoroamidodithionite, according to claim
 6. 